Fungicidal mixtures based on carbamate derivatives and insecticides

ABSTRACT

The present invention relates to mixtures comprising as active components 
     a) carbamate derivatives of the formula I 
     
       
         
         
             
             
         
       
         
         
           
             in which the substituents and the index have the following meaning: 
             T is CH or N 
             n is 0, 1 or 2 
             R is halogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl, it being possible for the radicals R to be different when n is 2,
 
and
 
b) at least one compound of the formula II

The present invention relates to mixtures comprising as activecomponents

a) carbamate derivatives of the formula I

-   -   in which the substituents and the index have the following        meaning:    -   T is CH or N    -   n is 0, 1 or 2    -   R is halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl, it being possible        for the radicals R to be different when n is 2,        and        b) at least one compound of the formula II

-   -   in which R₁ is C₁-C₄-alkyl or C₁-C₄-haloalkyl.

The combating of harmful phytopathogenic fungi is in many regions notthe only problem the farmer has to face. Also harmful insects can causea great damage to crops and other plants.

Thus, an efficient combination of fungicidal and insecticidal activityis desirable to overcome this problem.

Thus, it is an object of the present invention to provide a mixturewhich, on the one hand, has good fungicidal activity, and, on the otherhand, good insecticidal activity, resulting in a broader pesticidalspectrum of action. More particularly, the subject of the presentinvention is a mixture for protecting plants against diseases andinsects, characterized in that it comprises an effective amount of afungicide and at least an effective amount of an insecticide.Furthermore it is an object of the present invention to provide aprocess for treating plants using these mixtures.

We have found that this object is achieved by a mixture comprising asactive components

a) carbamate derivatives of the formula I

-   -   in which the substituents and the index have the following        meaning:    -   T is CH or N    -   n is 0, 1 or 2    -   R is halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl, it being possible        for the radicals R to be different when n is 2,    -   and        b) at least one compound of the formula II

-   -   in which R₁ is C₁-C₄-alkyl or C₁-C₄-haloalkyl.

Furthermore we have found a process for treating plants using thesemixtures.

The compounds of the formula I, their preparation and their actionagainst harmful fungi have been disclosed in the literature (WO-A96/01256 and WO-A 96/01258).

The compounds II, their preparation and their action against harmfulinsects has also been disclosed (EP 295 117).

Preferably, the compounds of formula I represent carbamate derivativesin which the combination of the substituents corresponds to one line oftable 1 which follows:

TABLE 1 No. T R_(n) I.1 N 2-F I.2 N 3-F I.3 N 4-F I.4 N 2-Cl I.5 N 3-ClI.6 N 4-Cl I.7 N 2-Br I.8 N 3-Br I.9 N 4-Br I.10 N 2-CH₃ I.11 N 3-CH₃I.12 N 4-CH₃ I.13 N 2-CH₂CH₃ I.14 N 3-CH₂CH₃ I.15 N 4-CH₂CH₃ I.16 N2-CH(CH₃)₂ I.17 N 3-CH(CH₃)₂ I.18 N 4-CH(CH₃)₂ I.19 N 2-CF₃ I.20 N 3-CF₃I.21 N 4-CF₃ I.22 N 2,4-F₂ I.23 N 2,4-Cl₂ I.24 N 3,4-Cl₂ I.25 N 2-Cl,4-CH₃ I.26 N 3-Cl, 4-CH₃ I.27 CH 2-F I.28 CH 3-F I.29 CH 4-F I.30 CH2-Cl I.31 CH 3-Cl I.32 CH 4-Cl I.33 CH 2-Br I.34 CH 3-Br I.35 CH 4-BrI.36 CH 2-CH₃ I.37 CH 3-CH₃ I.38 CH 4-CH₃ I.39 CH 2-CH₂CH₃ I.40 CH3-CH₂CH₃ I.41 CH 4-CH₂CH₃ I.42 CH 2-CH(CH₃)₂ I.43 CH 3-CH(CH₃)₂ I.44 CH4-CH(CH₃)₂ I.45 CH 2-CF₃ I.46 CH 3-CF₃ I.47 CH 4-CF₃ I.48 CH 2,4-F₂ I.49CH 2,4-Cl₂ I.50 CH 3,4-Cl₂ I.51 CH 2-Cl, 4-CH₃ I.52 CH 3-Cl, 4-CH₃

More preferred are compounds I.12, I.23, I.32 and I.38, particularlypreferred is compound I.32.

The compounds of formula II represent phenylpyrazoles, in which R₁ isC₁-C₄-alkyl or C₁-C₄-haloalkyl, preferably ethyl (common name:ethiprole) or trifluormethyl (common name: fipronil), more preferablytrifluormethyl.

The compounds of formulae I and II are capable of forming salts oradducts with inorganic or organic acids or with metal ions.

Examples of inorganic acids are hydrohalic acids, such as hydrogenfluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide,sulfuric acid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid, carbonic acid andalkanoic acids, such as acetic acid, trifluoroacetic acid,trichloroacetic acid and propionic acid, and also glycolic acid, lacticacid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalicacid, p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid,2-phenoxybenzoic acid or 2-acetoxybenzoic acid.

Suitable metal ions are in particular the ions of the elements of thefirst to eighth transition group, especially chromium, manganese, iron,cobalt, nickel, copper, zinc, and additionally those of the second maingroup, especially calcium and magnesium, and of the third and fourthmain group, in particular aluminum, tin and lead. If appropriate, themetals can be present in the different valencies that they can assume.

When preparing the mixtures, it is preferred to employ the substantiallypure, especially the pure active compounds of formulae I and II, towhich further active ingredients against harmful fungi or against otherpests, such as insects or nematodes, can be added. Thus, a furtheractive ingredient can be optionally added, for example at least oneadditional insecticide or fungicide, preferably an additional fungicide.

Preferred insecticides are those selected from the group consisting of

-   -   organophosphates such as acephate, azinphos-methyl,        chlorpyrifos, chlorfenvinphos, diazinon, dichlorvos,        dicrotophos, dimethoate, disulfoton, ethion, fenitrothion,        ffenthion, isoxathion, malathion, methamidophos, methidathion,        methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl,        paraoxon, parathion, phenthoate, phosalone, phosmet,        phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos,        prothiofos, sulprophos, triazophos, trichlorfon;    -   carbamates such as alanycarb, benfuracarb, carbaryl,        carbosulfan, fenoxycarb, furathiocarb, indoxacarb, methiocarb,        methomyl, oxamyl, Pirimicarb, Propoxur, Thiodicarb, Triazamate,        Carbofuran;    -   pyrethroids such as Bifenthrin, Cyfluthrin, Cypermethrin,        Deltamethrin, esfenvalerate, ethofenprox, fenpropathrin,        fenvalerate, cyhalothrin, lambdacyhalothrin, permethrin,        silafluofen, tau-fluvalinate, tefluthrin, tralomethrin,        zetacypermethrin;    -   arthropod growth regulators such as a) chitin synthesis        inhibitors: benzoylureas: chlorfluazuron, diflubenzuron,        flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron,        teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox,        etoxazole, clofentazine; b) ecdysone antagonists: halofenozide,        methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen,        methoprene, fenoxycarb; d) lipid biosynthesis inhibitors:        spirodiclofen;    -   various such as abamectin, acequinocyl, acetamiprid, amitraz,        azadirachtin, bifenazate, cartap, chlorfenapyr, chlordimeform,        cyromazine, diafenthiuron, dinetofuran, diofenolan, emamectin,        endosulfan, fenazaquin, formetanate, formetanate hydrochloride,        hydramethylnon, imidacloprid, indoxacarb, pyridaben,        pymetrozine, spinosad, sulfur, tebufenpyrad, thiamethoxam, and        thiocyclam.

Preferred fungicides are those selected from the group consisting of

-   -   acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl;    -   amine derivatives such as aldimorph, dodine, dodemorph,        fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamin,        tridemorph;    -   anilinopyrimidines such as pyrimethanil, mepanipyrim or        cyrodinyl;    -   antibiotics such as cycloheximid, griseofulvin, kasugamycin,        natamycin, polyoxin or streptomycin;    -   azoles such as bitertanol, bromoconazole, cyproconazole,        difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole,        fluquiconazole, flusilazole, hexaconazole, imazalil,        metconazole, myclobutanil, penconazole, propiconazole,        prochloraz, prothioconazole, tebuconazole, triadimefon,        triadimenol, triflumizol, triticonazole, flutriafol;    -   dicarboximides such as iprodion, myclozolin, procymidon,        vinclozolin;    -   dithiocarbamates such as ferbam, nabam, maneb, mancozeb, metam,        metiram, propineb, polycarbamate, thiram, ziram, zineb;    -   heterocyclic compounds such as anilazine, benomyl, boscalid,        carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet,        dithianon, famoxadon, fenamidon, fenarimol, fuberidazole,        flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol,        probenazole, proquinazid, pyrifenox, pyroquilon, quinoxyfen,        silthiofam, thiabendazole, thifluzamid, thiophanate-methyl,        tiadinil, tricyclazole, triforine;    -   copper fungicides such as Bordeaux mixture, copper acetate,        copper oxychloride, basic copper sulfate;    -   nitrophenyl derivatives such as binapacryl, dinocap, dinobuton,        nitrophthalisopropyl;    -   phenylpyrroles such as fenpiclonil or fludioxonil;    -   sulfur    -   other fungicides such as acibenzolar-S-methyl, benthiavalicarb,        carpropamid, chlorothalonil, cyflufenamid, cymoxanil, dazomet,        diclomezin, diclocymet, diethofencarb, edifenphos, ethaboxam,        fenhexamid, fentin-acetate, fenoxanil, ferimzone, fluazinam,        fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene,        metrafenon, pencycuron, propamocarb, phthalide,        toloclofos-methyl, quintozene, zoxamid;    -   strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin,        kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin or        trifloxystrobin;    -   sulfenic acid derivatives such as captafol, captan,        dichlofluanid, folpet, tolylfluanid;    -   cinnemamides and analogs such as dimethomorph, flumetover or        flumorph.

More preferred fungicides are those selected from the group consistingof

-   -   acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl;    -   azoles such as bitertanol, bromoconazole, cyproconazole,        difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole,        fluquiconazole, flusilazole, hexaconazole, imazalil,        metconazole, myclobutanil, penconazole, propiconazole,        prochloraz, prothioconazole, tebuconazole, triadimefon,        triadimenol, triflumizol, triticonazole, flutriafol;    -   dicarboximides such as iprodion, myclozolin, procymidon,        vinclozolin;    -   dithiocarbamates such as ferbam, nabam, maneb, mancozeb, metam,        metiram, propineb, polycarbamate, thiram, ziram, zineb;    -   heterocyclic compounds such as anilazine, benomyl, boscalid,        carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet,        dithianon, famoxadon, fenamidon, fenarimol, fuberidazole,        flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol,        probenazole, proquinazid, pyrifenox, pyroquilon, quinoxyfen,        silthiofam, thiabendazole, thifluzamid, thiophanate-methyl,        tiadinil, tricyclazole, triforine;    -   other fungicides such as acibenzolar-S-methyl, benthiavalicarb,        carpropamid, chlorothalonil, cyflufenamid, cymoxanil, dazomet,        diclomezin, diclocymet, diethofencarb, edifenphos, ethaboxam,        fenhexamid, fentin-acetate, fenoxanil, ferimzone, fluazinam,        fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene,        metrafenon, pencycuron, propamocarb, phthalide,        toloclofos-methyl, quintozene, zoxamid;    -   strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin,        kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin or        trifloxystrobin; sulfenic acid derivatives such as captafol,        captan, dichlofluanid, folpet, tolylfluanid;    -   cinnemamides and analogs such as dimethomorph, flumetover or        flumorph.

Especially preferred fungicides are those selected from

-   -   metalaxyl;    -   bitertanol, bromoconazole, cyproconazole, difenoconazole,        dinitroconazole, epoxiconazole, fenbuconazole, fluquiconazole,        flusilazole, hexaconazole, imazalil, metconazole, myclobutanil,        penconazole, propiconazole, prochloraz, prothioconazole,        tebuconazole, triadimefon, triadimenol, triflumizol,        triticonazole,    -   flutriafol;    -   iprodione;    -   thiram;    -   benomyl, boscalid, carbendazin, carboxin, thiabendazole,        thiophanate-methyl;    -   metrafenone, penycuron;    -   dimoxystrobin;    -   captan; and    -   dimethomorph.

The most preferred fungicides are those selected fromthiophanate-methyl, benomyl, carbendazim and thiabendazole.

In another preferred embodiment the most preferred fungicides areselected from metalaxyl, triticonazole, carbetazin, boscalid andthiophanate-methyl.

An extraordinary preferred fungicide is metalaxyl.

In another preferred embodiment the extraordinary preferred fungicide istriticonazole.

In another preferred embodiment the extraordinary preferred fungicide iscarbetazin.

In another preferred embodiment the extraordinary preferred fungicide isboscalid.

In another preferred embodiment the extraordinary preferred fungicide isthiophanate-methyl.

In a preferred embodiment the mixture comprises the compound I.32 andfipronil.

In another preferred embodiment the mixture comprises the compound I. 32and ethiprole.

In a preferred embodiment the mixture comprises the compound I.32,fipronil and a further fungicide.

In another preferred embodiment the mixture comprises the compound I.32,fipronil and a further fungicide.

In another preferred embodiment the mixture comprises the compound I.32,fipronil and an acylalanine such as benalaxyl, metalaxyl, ofurace oroxadixyl, especially metalaxyl.

In another preferred embodiment the mixture comprises the compound I.32,fipronil and an azole such as bitertanol, bromoconazole, cyproconazole,difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole,fluquiconazole, flusilazole, hexaconazole, imazalil, metconazole,myclobutanil, penconazole, propiconazole, prochloraz, prothioconazole,tebuconazole, triadimefon, triadimenol, triflumizol, triticonazole orflutriafol, especially tritoconazole.

In another preferred embodiment the mixture comprises the compound I.32,fipronil and a dicarboximide such as iprodione, myclozolin, procymidonor vinclozolin, especially iprodione.

In another preferred embodiment the mixture comprises the compound I.32,fipronil and a dithiocarbamate such as ferbam, nabam, maneb, mancozeb,metam, metiram, propineb, polycarbamate, thiram, ziram or zineb,especially thiram.

In another preferred embodiment the mixture comprises the compound I.32,fipronil and a heterocyclic compound such as anilazine, benomyl,boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet,dithianon, famoxadon, fenamidon, fenarimol, fuberidazole, flutolanil,furametpyr, isoprothiolane, mepronil, nuarimol, probenazole,proquinazid, pyrifenox, pyroquilon, quinoxyfen, silthiofam,thiabendazole, thifluzamid, thiophanate-methyl, tiadinil, tricyclazoleor triforine; especially benomyl, boscalid, carbendazin, carboxin,thiabendazole or thiophanate-methyl. In particular the mixture comprisesthe compound I.32, fipronil and boscalid. Also in particular the mixturecomprises the compound I.32, fipronil and carbentazin. Also I inparticular the mixture comprises the compound I.32, fipronil andthiophanate-methyl.

In another preferred embodiment the mixture comprises the compound I.32,fipronil and a further fungicide other fungicides such asacibenzolar-S-methyl, benthiavalicarb, carpropamid, chlorothalonil,cyflufenamid, cymoxanil, dazomet, diclomezin, diclocymet, diethofencarb,edifenphos, ethaboxam, fenhexamid, fentin-acetate, fenoxanil, ferimzone,fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene,metrafenon, pencycuron, propamocarb, phthalide, toloclofos-methyl,quintozene or zoxamid, especially metrafenone or penycuron.

In another preferred embodiment the mixture comprises the compound I.32,fipronil and a strobilurin such as azoxystrobin, dimoxystrobin,fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin,picoxystrobin or trifloxystrobin; especially dimoxystrobin.

In another preferred embodiment the mixture comprises the compound I.32,fipronil and a sulfenic acid derivative such as captafol, captan,dichlofluanid, folpet or tolylfluanid, especially captan.

In another preferred embodiment the mixture comprises the compound I.32,fipronil and a cinnemamide or ananalog thereof such as dimethomorph,flumetover or flumorph, especially dimethomorph.

In another preferred embodiment the mixture comprises two activeingredients only. The respective preferred embodiments are in accordancewith the above-mentioned ones.

In another preferred embodiment the mixture comprises three activeingredients only. The respective preferred embodiments are in accordancewith the above-mentioned ones.

In a preferred embodiment, the mixtures according to the invention areused for combating harmful fungi and harmful insects or nematodes.

In a further preferred embodiment, the mixtures according to theinvention are used for combating harmful fungi.

In a further preferred embodiment, the mixtures according to theinvention are used for combating harmful insects or nematodes.

In a further particular preferred embodiment, the mixtures according tothe invention comprise the compounds of formula I and formula II in asynergistic effective amount and are used for combating harmful fungi.

In a further particular preferred embodiment, the mixtures according tothe invention comprise the compounds of formula I and formula II in asynergistic effective amount and are used for combating harmful insectsor nematodes.

The mixtures according to the invention are especially important forcontrolling a large number of fungi and insects or nematodes on avariety of crop plants such as wheat, corn, rye, barley, oats, sorghum,rice, maize, grass, bananas, cotton, soy beans, coffee, sugar cane,grapevines, fruit species, ornamentals and vegetables such as cucumbers,beans, drybeans, tomatoes, potatoes, lettuce, cucurbits, cabbage,carrots, cruciferous, sunflowers and cucurbits, and on the seeds ofthese plants or on pasture and on seeds of pasture. In a specialembodiment the mixtures according to the present invention are appliedon soybeans. In another preferred embodiment the mixtures according thepresent invention are applied on seeds. In a particular embodiment themixtures according to the present invention are applied on seeds ofsoybeans.

Specifically, they are suitable for controlling the following harmfulfungi:

-   -   Alternaria species on vegetables and fruit,    -   Bipolaris and Drechslera species on cereals, rice and turf,    -   Blumeria graminis (powdery mildew) on cereals,    -   Botrytis cinerea (gray mold) on strawberries, vegetables,        ornamentals and grapevines,    -   Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,    -   Fusarium and Verticillium species on various plants,    -   Mycosphaerella species on cereals, bananas and peanuts,    -   Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans    -   Phytophthora infestans on potatoes and tomatoes,    -   Plasmopara viticola on grapevines,    -   Podosphaera leucotricha on apples,    -   Pseudocercosporella herpotrichoides on wheat and barley,    -   Pseudoperonospora species on hops and cucumbers,    -   Puccinia species on cereals,    -   Pyricularia oryzae on rice,    -   Rhizoctonia species on cotton, rice and turf,    -   Septoria tritici and Stagonospora nodorum on wheat,    -   Uncinula necator on grapevines,    -   Ustilago species on cereals and sugar cane, and    -   Venturia species (scab) on apples and pears.

They are also suitable for controlling the following harmful insectsfrom the order of the

-   -   lepidopterans (Lepidoptera), for example Agrotis ypsilon,        Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis,        Argyresthia conjugella, Autographa gamma, Bupalus piniarius,        Cacoecia murinana, Capua reticulana, Chematobia brumata,        Choristoneura fumiferana, Choristoneura occidentalis, Cirphis        unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania        nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus        lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia        subterranea, Galleria mellonella, Grapholitha funebrana,        Grapholitha molesta, Heliothis armigera, Heliothis virescens,        Heliothis zea, HeHula undalis, Hibernia defoliaria, Hyphantria        cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina        fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera        scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege        sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia        clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia        pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora        gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea        operculella, Phyllocnistis citrella, Pieris brassicae,        Plathypena scabra, Plutella xylostella, Pseudoplusia includens,        Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga        cerealella, Sparganothis pilleriana, Spodoptera frugiperda,        Spodoptera littoralis, Spodoptera litura, Thaumatopoea        pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera        canadensis,    -   beetles (Coleoptera), for example Agrilus sinuatus, Agriotes        lineatus, Agriotes obscurus, Amphimallus solstitialis,        Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum,        Atomaria linearis, Blastophagus piniperda, Blitophaga undata,        Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus        betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus        assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus        vespertinus, Crioceris asparagi, Diabrotica longicornis,        Diabrotica 12-punctata, Diabrotica virgifera, Epilachna        varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis,        Hylobius abietis, Hypera brunneipennis, Hypera postica, 1 ps        typographus, Lema bilineata, Lema melanopus, Leptinotarsa        decemlineata, Limonius californicus, Lissorhoptrus oryzophilus,        Melanotus communis, Meligethes aeneus, Melolontha hippocastani,        Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus,        Otiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta        chrysocephala, Phyllophaga sp., Phyllopertha horticola,        Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica,        Sitona lineatus and Sitophilus granaria,    -   dipterans (Diptera), for example Aedes aegypti, Aedes vexans,        Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata,        Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria,        Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens,        Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia        canicularis, Gasterophilus intestinalis, Glossina morsitans,        Haematobia irritans, Haplodiplosis equestris, Hylemyia platura,        Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii,        Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria        pectoralis, Mayetiola destructor, Musca domestica, Muscina        stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami,        Phorbia antiqua, Phorbia brassicae, Phorbia coarctata,        Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula        oleracea and Tipula paludosa,    -   thrips (Thysanoptera), e.g. Frankliniella fusca, Frankliniella        occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips        oryzae, Thrips palmi and Thrips tabaci,    -   hymenopterans (Hymenoptera), e.g. Athalia rosae, Atta        cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta,        Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata        and Solenopsis invicta,    -   heteropterans (Heteroptera), e.g. Acrosternum hilare, Blissus        leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus,        Dysdercus intermedius, Eurygaster integriceps, Euschistus        impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus        pratensis, Nezara viridula, Piesma quadrata, Solubea insularis        and Thyanta perditor,    -   homopterans (Homoptera), e.g. Acyrthosiphon onobrychis, Adelges        laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis        pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri,        Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum,        Aulacorthum solani, Brachycaudus cardui, Brachycaudus        helichrysi, Brachycaudus persicae, Brachycaudus prunicola,        Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii,        Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia        nordmannianae, Dreyfusia piceae, Dysaphis radicola,        Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis        pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae,        Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae,        Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum,        Myzodes persicae, Myzus ascalonicus, Myzus cerasi, Myzus        varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus        bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla        mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum        maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis        mala, Sappaphis mali, Schizaphis graminum, Schizoneura        lanuginosa, Sitobion avenae, Trialeurodes vaporariorum,        Toxoptera aurantiiand, and Viteus vitifolii.    -   termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes        flavipes, Reticulitermes lucifugus and Termes natalensis,    -   orthopterans (Orthoptera), e.g. Acheta domestica, Blatta        orientalis, Blattella germanica, Forficula auricularia,        Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus        bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus,        Melanoplus sanguinipes, Melanoplus spretus, Nomadacris        septemfasciata, Periplaneta americana, Schistocerca americana,        Schistocerca peregrina, Stauronotus maroccanus and Tachycines        asynamorus,    -   Arachnoidea, such as arachnids (Acarina), e.g. of the families        Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma        americanum, Amblyomma variegatum, Argas persicus, Boophilus        annulatus, Boophilus decoloratus, Boophilus microplus,        Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes        rubicundus, Ornithodorus moubata, Otobius megnini, Dermanyssus        gaffinae, Psoroptes ovis, Rhipicephalus appendiculatus,        Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp.        such as Aculus schlechtendali, Phyllocoptrata oleivora and        Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus        pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such        as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus        cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus,        Tetranychus telarius and Tetranychus urticae, Panonychus ulmi,        Panonychus citri, and oligonychus pratensis;

They are furthermore suitable for controlling the following harmfulnematodes, especially plant parasitic nematodes such as root knotnematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogynejavanica, and other Meloidogyne species; cystforming nematodes,Globodera rostochiensis and other Globodera species; Heterodera avenae,Heterodera glycines, Heterodera schachtii, Heterodera trifolii, andother Heterodera species; Seed gall nematodes, Anguina species; Stem andfoliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimuslongicaudatus and other Belonoaimus species; Pine nematodes,Bursaphelenchus xylophilus and other Bursaphelenchus species; Ringnematodes, Criconema species, Criconemella species, Criconemoidesspecies, Mesocriconema species; Stem and bulb nematodes, Ditylenchusdestructor, Ditylenchus dipsaci and other Ditylenchus species; Awlnematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchusmulticinctus and other Helicotylenchus species; Sheath and sheathoidnematodes, Hemicycliophora species and Hemicriconemoides species;Hirshmanniella species; Lance nematodes, Hoploaimus species; falserootknot nematodes, Nacobbus species; Needle nematodes, Longidoruselongatus and other Longidorus species; Lesion nematodes, Pratylenchusneglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchusgoodeyi and other Pratylenchus species; Burrowing nematodes, Radopholussimilis and other Radopholus species; Reniform nematodes, Rotylenchusrobustus and other Rotylenchus species; Scutellonema species; Stubbyroot nematodes, Trichodorus primitivus and other Trichodorus species,Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni,Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrusnematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; andother plant parasitic nematode species.

The compounds of formulae I and II and optionally the further activeingredient(s) can be applied simultaneously, that is jointly orseparately, or in succession; the sequence, in the case of separateapplication, generally not having any effect on the result of thecontrol measures.

The compounds of formulae I and II are usually applied in an effectiveamount, preferably in a weight ratio of from 100:1 to 1:100, inparticular from 20:1 to 1:20, preferably from 10:1 to 1:10.

The compounds of formula I and the further fungicide are usually appliedin an effective amount, preferably in a weight ratio of from 1000:1 to1:1000.

Depending on the desired effect, the application rates of the mixturesaccording to the invention are, especially in the case of areas underagricultural cultivation, from 5 to 2 000 g/ha, preferably from 50 to 1500 g/ha, in particular from 50 to 750 g/ha.

Here, the application rates of the compounds of formula I are from 1 gto 1 kg/ha, preferably from 10 to 900 g/ha, in particular from 20 to 750g/ha.

Correspondingly, the application rates of the compounds of formula IIare from 1 g to 1 kg/ha, preferably from 10 to 750 g/ha, in particularfrom 20 to 500 g/ha.

Correspondingly, the application rates of the further fungicide are from1 g to 1 kg/ha, preferably from 5 to 900 g/ha, in particular from 10 to750 g/ha.

In the treatment of seed, the application rates of the mixture accordingto the invention are generally from 0.1 to 1 000 g/100 kg of seed,preferably from 0.1 to 200 g/100 kg, in particular from 1 to 100 g/100kg.

A further embodiment of the present invention is directed to the seedsbeing treated with the mixture according to the present invention.

In the control of phytopathogenic harmful fungi and/or harmful insectsand/or nematodes, especially in the control of phytopathogenic harmfulfungi and/or harmful insects, the separate or joint application of thecompounds of formulae I and II and optionally of the further activeingredient or of a mixture according to the invention is carried out bytreating the seeds, the plants or the soils before or after sowing ofthe plants or before or after emergence of the plants.

The mixtures according to the invention can be prepared, for example, inthe form of directly sprayable solutions, powders and suspensions or inthe form of highly concentrated aqueous, oily or other suspensions,dispersions, emulsions, oil dispersions, pastes, dusts, compositions forspreading or granules, and be applied by spraying, atomizing, dusting,broadcasting or watering or colored suspension, solution, emulsion to beapplied as such or as water based slurry with seed treatment machinery.The use form depends on the particular purpose; in each case, it shouldensure a distribution of the mixture according to the invention, whichis as fine and uniform as possible.

The formulations are prepared in a known manner, for example byextending the active compound with solvents and/or carriers, if desiredusing emulsifiers and dispersants. Solvents/auxiliaries which aresuitable are essentially:

-   -   water, aromatic solvents (for example Solvesso products,        xylene), paraffins (for example mineral fractions), alcohols        (for example methanol, butanol, pentanol, benzyl alcohol),        ketones (for example cyclohexanone, gamma-butyrolactone),        pyrrolidones (NMP, NOP), DMSO, acetates (glycol diacetate),        glycols, fatty acid dimethylamides, fatty acids and fatty acid        esters. In principle, solvent mixtures may also be used.    -   carriers such as ground natural minerals (for example kaolins,        clays, talc, chalk) and ground synthetic minerals (for example        highly disperse silica, silicates); emulsifiers such as nonionic        and anionic emulsifiers (for example polyoxyethylene fatty        alcohol ethers, alkylsulfonates and arylsulfonates) and        dispersants such as lignin-sulfite waste liquors and        methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammoniumsalts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids andsulfated fatty alcohol glycol ethers, furthermore condensates ofsulfonated naphthalene and naphthalene derivatives with formaldehyde,condensates of naphthalene or of naphthalenesulfonic acid with phenoland formaldehyde, polyoxyethylene octylphenyl ether, ethoxylatedisooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers,tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether,alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxidecondensates, ethoxylated castor oil, polyoxyethylene alkyl ethers,ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal,sorbitol esters, lignosulfite waste liquors and methylcellulose andethyleneoxide/propyleneoxide block copolymers.

For seed treatment, also regulators such as Azosprillium species andBradyrhizobium species such as Bradyrhizobium japonicum can be added tothe mixtures according to the present invention.

For seed treatment, also pigments can be added. Suitable pigments forseed treatment are pigment blue 15:3, pigment yellow 1, pigment red 112,pigment red 48:2, pigment red 57:1, Pigment red 53:1, pigment orange 43,pigment orange 5, pigment green 36, pigment green 7, pigment white 6.

Substances which are suitable for the preparation of directly sprayablesolutions, emulsions, pastes or oil dispersions are mineral oilfractions of medium to high boiling point, such as kerosene or dieseloil, furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, for example toluene,xylene, parafin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, methanol, ethanol, propanol, butanol, cyclohexanol,cyclohexanone, isophorone, strongly polar solvents, for example dimethylsulfoxide, N-methylpyrrolidone and water.

Powders, materials for spreading and dustable products can be preparedby mixing or concomitantly grinding the active substances with a solidcarrier.

Granules, for example coated granules, impregnated granules andhomogeneous granules, can be prepared by binding the active compounds tosolid carriers. Examples of solid carriers are mineral earths such assilica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk,bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials,fertilizers, such as, for example, ammonium sulfate, ammonium phosphate,ammonium nitrate, ureas, and products of vegetable origin, such ascereal meal, tree bark meal, wood meal and nutshell meal, cellulosepowders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active compounds. Theactive compounds are employed in a purity of from 90% to 100%,preferably 95% to 100% (according to NMR spectrum).

The following are examples of formulations:

1. Products for Dilution with Water

A) Water-Soluble Concentrates (SL, LS)

10 parts by weight of the active compounds are dissolved in water or ina water-soluble solvent. As an alternative, wetters or other auxiliariesare added. The active compound dissolves upon dilution with water.

B) Dispersible Concentrates (DC)

20 parts by weight of the active compounds are dissolved incyclohexanone with addition of a dispersant, for examplepolyvinylpyrrolidone. Dilution with water gives a dispersion.

C) Emulsifiable Concentrates (EC)

15 parts by weight of the active compounds are dissolved in xylene withaddition of calcium dodecylbenzenesulfonate and castor oil ethoxylate(in each case 5% strength). Dilution with water gives an emulsion.

D) Emulsions (EW, EO, ES)

40 parts by weight of the active compounds are dissolved in xylene withaddition of calcium dodecylbenzenesulfonate and castor oil ethoxylate(in each case 5% strength). This mixture is introduced into water bymeans of an emulsifier machine (Ultraturvax) and made into a homogeneousemulsion. Dilution with water gives an emulsion.

E) Suspensions (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of the active compounds arecomminuted with addition of dispersant, wetters and water or an organicsolvent to give a fine active compound suspension. Dilution with watergives a stable suspension of the active compound.

F) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

50 parts by weight of the active compounds are ground finely withaddition of dispersants and wetters and made into water-dispersible orwater-soluble granules by means of technical appliances (for exampleextrusion, spray tower, fluidized bed). Dilution with water gives astable dispersion or solution of the active compound.

G) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, WS)

75 parts by weight of the active compounds are ground in a rotor-statormill with addition of dispersant, wetters and silica gel. Dilution inwater gives a stable dispersion or solution with the active compound.

2. Products to be Applied Undiluted H) Dustable Powders (DP, DS)

5 parts by weight of the active compounds are ground finely and mixedintimately with 95% of finely divided kaolin. This gives a dustableproduct.

I) Granules (GR, FG, GG, MG)

0.5 parts by weight of the active compounds is ground finely andassociated with 95.5% carriers. Current methods are extrusion,spray-drying or the fluidized bed. This gives granules to be appliedundiluted.

J) ULV Solutions (UL)

10 parts by weight of the active compounds are dissolved in an organicsolvent, for example xylene. This gives a product to be appliedundiluted.

The active compounds can be used as such, in the form of theirformulations or the use forms prepared therefrom, for example in theform of directly sprayable solutions, powders, suspensions ordispersions, emulsions, oil dispersions, pastes, dustable products,materials for spreading, or granules, by means of spraying, atomizing,dusting, spreading or pouring. The use forms depend entirely on theintended purposes; it is intended to ensure in each case the finestpossible distribution of the active compounds according to theinvention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances, as suchor dissolved in an oil or solvent, can be homogenized in water by meansof a wetter, tackifier, dispersant or emulsifier. Alternatively, it ispossible to prepare concentrates composed of active substance, wetter,tackifier, dispersant or emulsifier and, if appropriate, solvent or oil,and such concentrates are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations canbe varied within relatively wide ranges. In general, they are from0.0001 to 10%, preferably from 0.01 to 1%.

The active compounds may also be used successfully in theultra-low-volume process (ULV), it being possible to apply formulationscomprising over 95% by weight of active compound, or even to apply theactive compound without additives.

Various types of oils, wetters, adjuvants, herbicides, fungicides, otherpesticides, or bactericides may be added to the active compounds, ifappropriate just immediately prior to use (tank mix). These agents canbe admixed with the agents according to the invention in a weight ratioof 1:10 to 10:1.

The mixtures according to the invention or the correspondingformulations comprising a mixture according to the invention are appliedby treating the harmful fungi, their habitat or the plants, seeds,soils, areas, materials or spaces to be kept free from them and theinsects or nematodes or their food supply, habitat or breeding groundswith a fungicidally and insecticidally effective amount of the mixtureaccording to the invention or, in the case of separate application, ofthe compounds of formulae I and II and optionally at least a furtheractive ingredient.

The mixtures according to the invention or the correspondingformulations comprising a mixture according to the invention are appliedby treating the harmful fungi, their habitat or the plants, seeds,soils, areas, materials or spaces to be kept free from them with afungicidally effective amount of the mixture according to the inventionor, in the case of separate application, of the compounds of formulae Iand II and optionally at least a further active ingredient.

The mixtures according to the invention or the correspondingformulations comprising a mixture according to the invention are appliedby treating the insects or nematode or their food supply, habitat orbreeding grounds with a insecticidally effective amount of the mixtureaccording to the invention or, in the case of separate application, ofthe compounds of formulae I and II and optionally at least a furtheractive ingredient.

The testing of the mixtures according to the present invention showsthat said mixtures are effective in controlling fungi and/or insectsand/or nematodes.

We claim:
 1. Seed treated with a mixture of: a) carbamate derivatives ofthe formula I

in which the substituents and the index have the following meaning: T isCH or N; n is 0, 1 or 2; and R is halogen, C₁-C₄-alkyl orC₁-C₄-haloalkyl, it being possible for the radicals R to be differentwhen n is 2, and b) at least one compound of the formulae II

in which R₁ is C₁-C₄-alkyl or C₁-C₄-haloalkyl, in an amount of from 1 to1,000 g/100 kg.
 2. The seed of claim 1, wherein R₁ is trifluoromethyl.3. The seed of claim 1, wherein R₁ is ethyl.
 4. The seed of claim 1,wherein the mixture further comprises a fungicide.
 5. The seed of claim4, wherein the fungicide is metalaxyl, triticonazole, carbetazin,boscalid or thiophanate-methyl.
 6. The seed of claim 1, wherein theweight ratio of the compound of formula I to compound of formula II isfrom 100:1 to 1:100.
 7. The seed of claim 6, wherein the weight ratio ofthe compounds of formula I to the fungicide is from 1000:1 to 1:1000.